CN1483010A - Production of olefin dimers and oligomers - Google Patents

Production of olefin dimers and oligomers Download PDF

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CN1483010A
CN1483010A CNA02803385XA CN02803385A CN1483010A CN 1483010 A CN1483010 A CN 1483010A CN A02803385X A CNA02803385X A CN A02803385XA CN 02803385 A CN02803385 A CN 02803385A CN 1483010 A CN1483010 A CN 1483010A
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alkene
product
olefines
compositions
octene
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CN100439302C (en
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Gi
G·玛瑟斯
J·S·古斯马克
M·詹森
L·R·马滕斯
H·J·拜克尔斯
A
E·T·A·范德里斯奇
I
R·F·I·卡尔斯
J·R·舒特
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ExxonMobil Chemical Patents Inc
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Abstract

A method of making a higher olefin product from a C4<+> fraction separated from the hydrocarbon product produced by an oxygenate to olefin reaction unit. The C4<+> fraction primarily contains butenes which may be directed to a higher olefin reaction unit without removing isobutenes, butanes, and/or butadiene. The C4<+> fraction is particularly well suited for the production of higher olefins because of its high olefin content, low branching number, and low contaminent levels. The invention is also directed to an olefin product composition that is produced by contacting the C4<+> fraction with an oligomerization catalyst. The olefin composition is characterized by a relatively high octene content, and octene with a branching number less than 1.4.

Description

The preparation of higher alkene
Invention field
The olefin production alkene derivatives that the present invention relates to be produced by oxide compound is the system of higher alkene.Described then higher alkene can be used to prepare various alkene derivatives products, comprises alcohol, aldehyde, acid and ester.
Background of invention
Alkene such as butylene and amylene can be used for preparing the end product of multiple derivative.The example of these end products comprises alcohol, aldehyde, acid and ester.Thereby butylene and amylene can also be formed the higher alkene with eight or more a plurality of carbon by oligomerization.Described higher alkene can be straight chain or they can have one or more alkyl branches.Described then higher alkene can be converted into alcohol, aldehyde, acid and ester.
The butylene that is used to prepare the alkene derivatives product promptly produces low molecular weight hydrocarbon by high-molecular-weight hydrocarbons and prepares usually by the cracking hydrocarbon feed.The cracking of hydrocarbon feed can catalysis or on-catalytic finish.For example at people's such as Hallee US 3,407,789, the US3 of Woebcke, 820,955, described the on-catalytic cracking process among people's such as the US 4,499,055 of DiNicolantonio and Gartside the US 4,814,067.At Cormier, people's such as Jr. US4,828,679, people's such as Rabo people's such as US 3,647,682, Rosinski US3,758,403, people's such as Gartside people's such as US 4,814,067, Li US4,980,053 and people's such as Yongqing US 5,326,465 in catalytic pyrolysis process has been described.
A problem using hydrocarbon pyrolysis device production alkene is the alkene that alkene contains a lot of alkyl branchesization.For example in the butylene logistics, iso-butylene must at first be removed before butylene is introduced in the oligomerizing device.In butene feed, exist iso-butylene can cause forming the higher alkene of collateralization, and the latter can cause branched-chain alcoho.And branched-chain alcoho has low relatively commercial value because it can generate poor softening agent.
Another problem of using the alkene of hydrocarbon pyrolysis device production is that described alkene contains a large amount of sulphur and nitrogen compound.These compounds make an acidic catalyst inactivation of using in alkene derivatization process such as olefin oligomerization reaction process.People's such as the US 5,432,243 of Bodart and Debras US 4,861 for example, if disclosing impurity in 939 need not remove by other purifier apparatus, then arsenic and carbon oxysulfide (COS) may have problems in the alkene derivatization process.In people's such as Gurak US 5,146,042, proposed at C 2-C 4Sulphur impurity in the alkene may cause occurring undesirable side reaction in higher alkene and alkene derivatization process.This alkene purifying needs at first impurity to be extracted in the selected hydrocarbon, and rectifying goes out clean light olefin from hydrocarbon then.Nickel catalyzator can be used to remove sulphur impurity in addition.It is very big to remove the common scale of sulphur devices needed from alkene, and it is very expensive to operate.
According to applied hydrocarbon feed in the cracker, may need other lock out operation, as the removing of diolefine, removing of different-alkene and/or removing of paraffinic hydrocarbons.As an example, contain the divinyl and the iso-butylene that must remove in a large number in the butylene logistics from hydrocarbon pyrolysis device.In people's such as Vora US 6,049,017, divinyl removes by control hydrogenation process.Described iso-butylene is by making the butylene logistics contact and catalytic eliminating with methyl alcohol in methyl tertiary butyl ether (MTBE) reactor.Described iso-butylene is converted into MTBE, and n-butene and butane are by the MTBE reactor.N-butene and butane are introduced in the butane cracking device and go to produce ethene and propylene or to be incorporated in the oligomerizing device then.
In the preparation process of higher alkene,, from the butylene logistics, do not remove butane usually because application is once passed through or the higher alkene process of low internal circulating load.But make butane and higher alkene product separation, the sepn process that this is easier and expense is lower.For example the olefin(e) centent from the butylene logistics of steam cracking device is generally about 60wt%.Under the per pass conversion of about 50%-70%, the butylene logistics is incorporated in the higher alkene device.Only have this moment a small amount of or not circulation, so butane is easy to and the higher alkene product separation.But this method has several shortcomings.The first, 30%-50% alkene is not converted into desirable product in the charging, thereby causes the process overall yield lower.The second, the process that per pass conversion is high can cause the selectivity of desirable alpha-olefin lower.Alpha-olefin is the alkene that contains carbon-to-carbon double bond between first and second carbon.
The process of high internal circulating load, low per pass conversion may overcome this two shortcomings.Thereby olefin(e) centent is acceptable level in the high olefin stream maintenance charging of olefin(e) centent but this process need obtains.Butylene logistics from cracker has low olefin(e) centent.If therefore use the process of high internal circulating load, low per pass conversion, then must from the butylene logistics, remove most of paraffinic hydrocarbons.Because the boiling range of component is approaching relatively, this subtractive process may be difficulty and expensive task.
According to the charging specification of process, removing various impurity atoies at preparation alkene derivatives product from olefin stream may be very difficult process technically.Therefore, if can access the low olefin stream of paraffinic hydrocarbons concentration, alkyl branches, diene and/or impurity concentration, thereby make paraffinic hydrocarbons and impurity removal process minimize or avoid these processes, the expense that then removes these components will minimize or eliminate fully.
Summary of the invention
The invention provides and a kind ofly prepare the higher alkene product, be specially the method for octene, nonene and laurylene mixture by oxide compound to the alkene that the process of alkene produces.This method comprises that thereby oxide compound is contacted with molecular sieve catalyst produces the hydrocarbon product contain alkene, isolates the C that contains four or more a plurality of carbon from described hydrocarbon product 4 +Cut, and make C 4 +Thereby contacting with the oligomerizing catalyzer, cut produces the product that contains higher alkene.Randomly, the part unreacting olefin that is not converted into product can return C 4 +In the cut.
Brief description of the drawings
By the detailed description of the present invention that reference is carried out in conjunction with the accompanying drawings, the present invention may be better understood, wherein:
Fig. 1 is a kind of embodiment of preparation higher alkene;
Fig. 2 is a kind of embodiment that the higher alkene product separation is become various olefin component.
The detailed description of invention
In order to reduce the relevant cost of preparation higher alkene, the present invention uses autoxidisable substance to the part hydrocarbon product of the device of alkene to prepare new C 4 +Hydrocarbon-fraction.Oxide compound to the device of alkene is preferably methyl alcohol-to-alkene (MTO) device.This C 4 +Cut contains above 60wt%, preferably surpasses the C of 80wt% 4 +Alkene.This C 4 +Cut has high relatively olefin(e) centent, promptly low paraffinicity, diene seldom and the low relatively alkene of collateralization degree.Olefin(e) centent surpasses or the olefin stream that equals about 60wt% is called as the olefin stream with high olefin content in the present invention.On the contrary, the olefin(e) centent olefin stream that is lower than about 60wt% is called as the olefin stream with low olefin-content.In addition, C 4 +Cut contains few relatively sulphur and nitrogen compound or not sulfur-bearing and nitrogen compound, and these materials tend to make applied oligomerizing catalyst deactivation in the higher alkene process.
The invention provides the higher alkene product that contains a large amount of octenes, nonene and laurylene.This then higher alkene can be used to prepare higher alcohols, and described higher alcohols can be used as the chemical feedstocks of multiple industrial softening agent.The advantage of this method is not need to use relatively costly alkene purifier apparatus, if perhaps use, when using desirable C 4 +During cut, need less purification devices.In big plant-scale process, this will cause the obvious reduction of equipment cost, and the obvious reduction of running cost.The reduction of this equipment and running cost finally offers the identical high-quality product of human consumer, but cost is obviously lower.
In the present invention, come autoxidisable substance to the hydrocarbon product of the reaction unit of alkene to be introduced in the tripping device known in the art, with number separate hydrocarbons according to carbon.For example, at first methane is separated from hydrocarbon product, isolated ethene and ethane (C subsequently 2Separate), be propylene and propane (C then 3Separate).The remainder of hydrocarbon product promptly mainly contains the part (C of four and five carbon 4 +Cut) is introduced into the higher alkene device.C can when beginning, isolated separation sequence in addition 4 +Cut, thus make C 2/ C 3The capacity requirement of tripping device reduces 10%-25%.
C 4 +Cut contains above 60wt%, preferably surpasses 80wt%, more preferably surpasses the hydrocarbon with four and five carbon of 90wt%.Described C 4 +Cut contains above 60wt%, preferably surpasses the alkene (C with four carbon of 80wt% 4Alkene).At C 4 +The example of the alkene that is contained in the cut is 1-butylene, cis and trans 2-butylene, iso-butylene and amylene.Described C 4 +Cut preferably contains 60-97wt%, more preferably the alkene of 80-97wt%.Described C 4 +The remainder of cut contains paraffinic hydrocarbons and few butadiene and other component.Desirable is C 4 +Cut more preferably has following compositing range: 70-95wt%, the n-butene of 80-95wt% more preferably, and described n-butene comprises 1-butylene and cis and trans 2-butylene; 2-8wt% preferably is lower than the iso-butylene of 6wt%; 0.2-5wt% preferably is lower than the butane of 3wt%; 2-10wt% preferably is lower than the amylene of 6wt%; And 2-10wt%, preferably be lower than propane and the propylene of 5wt%.
Also wish described alkene C 4 +Cut has low side chain number.Desirable is that average side chain number is lower than 2.0, preferably is lower than 1.6, more preferably less than 1.4.Average side chain number (ABN) is defined as follows:
ABN=1+ (1 *Single side chain+2*% two side chains of %)/the % total olefin
For example, if rare olefin stream has 20%1-butylene, 50%2-butylene, 10% butane, 10% iso-butylene, 5% propane and 5%3-methyl butene, then average side chain number is about 1.17.The ABN that contains the alkene of nearly 0% branched-chain alkene is about 1.0.
In one embodiment, C 4 +Cut can in statu quo be used, and that is to say directly to enter the higher alkene device from tripping device.In addition if desired, can be with C 4 +Cut carries out some other processing to it before being incorporated into the higher alkene device.This wherein can comprise hydrogenation process, is butylene if not all then making most of selectively hydrogenating butadiene, and makes the part selective isobutene be hydrogenated to Trimethylmethane.Thereby the amount of collateralization higher alkene product is reached is very important to the amount of iso-butylene at least in the restriction alkene charging.Preferably do not carrying out under the condition that divinyl or iso-butylene remove C 4 +Cut is introduced in the higher alkene device.
In another embodiment, C 4 +The purifying of cut may need to remove the impurity of low levels, and these impurity can disturb the processing property of higher alkene reaction unit and/or the performance of oxidation (hydroformylation) catalyzer.The impurity of low levels generally includes polar molecule.Its example comprises oxide compound such as water, ether, alcohol and carboxylic acid.These compounds can with various materials for example solid molecular sieves, extract and fractionation removes with all kinds of SOLVENTS.
C 4 +The content of the impurity of cut such as hydrogen sulfide, carbon oxysulfide and arsenic is very low usually.So C 4 +Cut can be through being incorporated in the higher alkene device behind minimum separation and the purifying.In fact, isolate C the hydrocarbon product from oxide compound to alkene 4 +Behind the cut, removing of hydrogen sulfide, carbon oxysulfide or arsenic is normally unnecessary.Desirable is C in per 1,000,000 weight parts 4 +The hydrogen sulfide content of cut is lower than 20 parts (ppmw), preferably is lower than 5ppmw, more preferably less than 1ppmw.Also wish C 4 +The carbon oxysulfide content of cut is lower than 20ppmw, preferably is lower than 5ppmw, more preferably less than 1ppmw.Similarly, wish C 4 +The arsenic content of cut is lower than 20ppmw, preferably is lower than 5ppmw, more preferably less than 1ppmw.
If desired olefin product stream is carried out other purifying, can use as " chemical encyclopedia " (Encyclopedia of ChemicalTechnology) at Kirk-Othmer, the 4th edition, the 9th volume, John Wiley ﹠amp; Sons, the purification system in 1996, the 894-899 pages or leaves, being described in here wherein introduced as reference.Also can use in addition as " chemical encyclopedia " (Encyclopedia ofChemical Technology) at Kirk-Othmer, the 4th edition, the 20th volume, John Wiley ﹠amp; Sons, the purification system in 1996, the 249-271 pages or leaves, description is wherein also here introduced as reference.
In another embodiment, do not separating hydrocarbon, do not separating the paraffinic hydrocarbons of alkene and same carbon number or C with different carbon numbers 4 +Cut is introduced the MTBE device to remove iso-butylene or to be incorporated into hydrogenation unit with under the situation that removes divinyl and/or iso-butylene, with C 4 +Cut is incorporated in the higher alkene device.Therefore with C 4 +Cut is incorporated into before the higher alkene device, and specific equipment is as being used for separation of C 4With C 5The rectifier unit of hydrocarbon or butylene and butane, MTBE device and hydrogenation unit all no longer need.
In another embodiment, in the higher alkene device, be not converted into the portion C of product 4 +Cut is directed getting back to C 4 +In the cut.Therefore the hydrocarbon charging that enters the higher alkene device will have and C 4 +The composition that cut is different.The hydrocarbon charging that enters the higher alkene device will comprise the hydrocarbon from recycle stream, and this recycle stream can compare C usually 4 +Cut contains more relatively paraffinic hydrocarbons.The compositing range that enters the hydrocarbon charging of higher alkene device depends on the reaction conditions in the specification of desirable higher alkene product, oligomerizing catalyzer, the oligomerizing device, the amount and the C of recycle hydrocarbons 4 +The composition of cut.
C 4 +The content of low paraffinic hydrocarbons and impurity provides flexibility of operation for the operation of the higher alkene process of high internal circulating load, low per pass conversion in the cut.The present invention is under the situation of the overall load that does not obviously increase higher alkene device and recovery system, and, allow to circulate from the unreacted alkene of higher alkene device not having under the dangerous situation of obviously accumulation of the impurity that can make the oligomerizing catalyst deactivation.Use the charging that paraffinicity is low and detrimental impurity content is low by higher hydrocarbon device, the overall productive rate of higher alkene product and isomer selectivity are obviously improved the process of using high internal circulating load, low per pass conversion.The higher alkene process of high internal circulating load, low per pass conversion can transform in its process and surpass 80%, often surpasses 90% alkene.In addition, high internal circulating load can provide bigger flexibility of operation, thereby optimizes the product selectivity to alpha-olefin such as 1-octene.
By comparison, the conventional once higher alkene process by, high conversion transforms during the course usually and is lower than 80%, often is lower than 70% alkene.In addition, because conventional higher alkene device operates under high relatively per pass conversion, cause the selectivity of the higher alkene product of more wishing to obtain lower.Desirable higher alkene product will contain more relatively alpha-olefin, and have low relatively side chain number.
The higher alkene process need of high internal circulating load, low per pass conversion obtains the high alkene charging of olefin(e) centent, thereby keeps the discharge volume minimum.In one embodiment, with butene content be the C of 70-97wt% 4 +Cut is incorporated in the higher alkene device.Described C 4 +Cut mixes with hydrocarbon from recycle stream, thereby produces the optimum hydrocarbon feed composition of higher alkene device.Described optimum hydrocarbon feed composition will be according to the internal circulating load in the higher alkene device and conversion of olefines per-cent and is changed.Described hydrocarbon feed composition can change between the butylene of 20-95wt%.Paraffinic hydrocarbons is used as thinner, thus the speed of reaction in the control higher alkene process.At C 4 +A small amount of paraffinic hydrocarbons in the cut can also make the volume minimum into the needed emission gases of inert substance content in the charging of control hydrocarbon.This will make the amount of alkene minimum of losing in the effluent streams.
The alkene per pass conversion of the process of high internal circulating load is 30%-70%, is preferably 40%-70%, more preferably 45%-70%.Total olefin conversion can be preferably 90%-98% up to 80%-98%.Another advantage of using the process of high internal circulating load, low per pass conversion is the selectivity of product, can be optimised as the isomer selectivity to the 1-octene.
A kind of embodiment of high internal circulating load process as shown in Figure 1.The C that produces to the device 10 of alkene at oxide compound 4 +Cut 12 is introduced in the higher alkene device 14.The product 16 that contains higher alkene and unreacting olefin and paraffinic hydrocarbons is introduced in the product separation device 15.Higher alkene product 17, promptly octene, nonene and laurylene separate with paraffinic hydrocarbons with unreacted alkene, are introduced into then in other the tripping device.These tripping devices are represented by 15b, 15c, 15d and 15e in Fig. 2.Purge stream 18 contains unreacted alkene and inert substance, comprises paraffinic hydrocarbons.Described purge stream 18 contains 40wt%-90wt% alkene.Part purge stream 18 is discharged by effluent streams 22, remain inert substance in the higher alkene device in specific compositing range thereby remain on, and this compositing range makes conversely the alkene in the hydrocarbon charging that enters higher alkene device 14 remain on desirable concentration.Remaining purge stream 18 is circulated back in the olefine reaction device 14 by recycle stream 26.
Another embodiment comprises that using one or more tripping devices is removed to small part paraffinic hydrocarbons and undesirable alkene from purge stream 18.The example of described olefin separation comprises rectifying tower equipment and absorption, extraction or membrane separation plant and their combination, and wherein said rectifying tower equipment comprises rectifier.Described olefin separation is preferably one or more fractionation plants.Described fractionation plant is preferably operated under the condition of not using poor physical solvent.The example of the compound that removes from purge stream 18 comprises butane and Trimethylmethane.After the desired portion of these compounds had been discharged from as effluent streams, the alkene after the desirable separation can be circulated back in the higher alkene device 14 by recycle stream 26.
After the total amount of paraffinic hydrocarbons that enters higher alkene device 14 and alkene has been determined, then according to desirable paraffinic hydrocarbons and the degree that removes of alkene and the mass rate that purge stream 18 is recently determined in the circulation in the process by alkene effluent streams 22.In a kind of preferred embodiment, in the purge stream 18 at least the paraffinic hydrocarbons of 50wt% remove 75wt% at least more preferably, and most preferably be 90wt% at least by effluent streams 22.If tripping device is arranged in the purge stream 18, the paraffinic hydrocarbons that then has bigger per-cent is removed.Effluent streams 22 preferably contains and is no more than 50wt%, more preferably is no more than 20wt%, and most preferably is the alkene that is no more than 5wt%.
Alkene recycle stream 26 preferably contains 50wt% at least and is included in alkene in the purge stream 18,75wt% at least more preferably, and most preferably be 90wt% at least.Remaining recovery olefin stream 26 can contain paraffinic hydrocarbons and other material that exists in purge stream 18.
If not whole, most of process then known in the art may be used to make C 4 +Cut is oligomeric to be combined into the higher alkene with eight or more a plurality of carbon.The solid phosphoric acid polyreaction is that the oligomerization of butenes of using usually closes reaction method.In this process, butylene is joined in many bed reactors that solid phosphoric acid is housed, and described solid phosphoric acid is made by phosphate mixture granulation and calcining on the diatomite.Described operational condition is 175 ℃-225 ℃ and reaches the pressure of 20atm at least.The selectivity of higher alkene is relatively low, and because this reason, this process often links with the petroleum refinement process, thereby guarantees the economic utilization of the product that these value are lower.Use landfill method processing catalyzer in addition and can have environmental problem and relevant cost.
Dimersol Be a kind of commercial run, this method is produced more normal olefine than phosphoric acid method.Under the described pressure condition that is reflected at 50 ℃-80 ℃ and about 1600kPa-1800kPa, use homogeneous phase nickel dialkyldithiocarbamate Al catalysts and in liquid phase, carry out.In product stream, inject ammonia and water with catalyst neutralisation, isolate hydrocarbon from aqueous phase then.Then with catalyst recovery and be circulated back in the reactor.
In another embodiment, modified ZSM-5-22 catalyzer can be used as the oligomerizing catalyzer.Verrelst etc. are at US 6,013, a kind of ZSM-22 olefin oligomerization reaction molecular sieve catalyst of modification has been described in 851, wherein molecular sieve contains metal-silicon core and upper layer, and upper layer has higher silicon metal ratio than core, US 6,013, and 851 disclosure is introduced the application as reference.Described metal is selected from aluminium, gallium and iron.This catalyzer has reduced the amount of the collateralization higher alkene that produces during the course.In addition, in the alkene charging, exist some paraffinic hydrocarbonss that the catalytic efficiency of catalyzer is not had or seldom influence is only arranged.Therefore at C 4 +The butane of relatively small amount needn't be separated from charging in the cut.For example can use 1: 1, be preferably 2: 1 butylene: the butane ratio.Show also that in addition a spot of water can improve the output of desirable higher alkene.
Applying modified ZSM-22 catalyzer in the higher alkene process of high internal circulating load can keep the product selectivity to octene under the situation that the side chain amount reduces.For example, use C 4 +Cut is as charging, and the octene selectivity can surpass 80%.Can reach when using higher recycle ratio and surpass 90% octene selectivity.Described oligomerizing can be 160 ℃-300 ℃ in temperature range, be preferably 170 ℃-260 ℃, and most preferably be 180 ℃-260 ℃, pressure range advantageously is 5MPa-10MPa, be preferably 6MPa-8MPa, and alkene hour air speed scope advantageously is 0.1hr -1-20hr -1, be preferably 0.5hr -1-10hr -1, and most preferably be 0.75hr -1-3.5hr -1Condition under carry out.
In another embodiment, C 4 +The oligomerizing of cut alkene can be people such as Saleh at US 5,254, and the nickel oxide described in 783 (NiO) carries out when catalyzer exists, and the disclosure of the document is here introduced as reference.Described catalyzer contains the amorphous NiO to disperse individual layer to exist on surface of silica support.Described carrier also contains the oxide compound of small amount of aluminum, gallium or indium, is about 4: 1 to about 100: 1 thereby make the NiO that exists in the catalyzer and the scope of the ratio of metal oxide.Described catalyzer is converted into the octene product with linear butenes, on average contains on wherein said each molecule of octene product to be lower than about 2.6, is usually less than 2.0-2.4 methyl group.
The NiO catalyzer forms the mixed polymerization reactor product of mainly being made up of octene in the butene dimerization reaction be effective especially.C 4 +OTO preferably contains the iso-butylene that is no more than 5wt%, because iso-butylene tends to form the high product of collateralization degree.By selective hydrogenation C 4 +OTO can reach desirable isobutylene concentration.The existence of paraffinic hydrocarbons is normally harmless in the alkene charging, if but its ratio rises to more than the 80wt%, and then this method can become very uneconomical.
The oligomerizing of using the NiO catalyzer carries out in liquid phase or gas phase.Temperature condition comprises 150 ℃-275 ℃ temperature, and the liquid hour weight feeding rate of butylene by catalyzer is 0.4hr in gas phase -1-1.8hr -1, be preferably 0.6hr -1-0.7hr -1When oligomerizing carries out in liquid phase and when catalyzer and olefin, alkene is preferably 2: 1 to 8: 1, more preferably 4: 1 to 6: 1 with the scope of the ratio of catalyzer.When oligomerizing approaching, for or be higher than when carrying out under the emergent pressure of alkene, to keep liquid phase be desirable by reacting when inertia high boiling hydrocarbon such as n-paraffin or naphthenic hydrocarbon exist.
In another embodiment, the ZSM-57 catalyzer can be used as the oligomerizing catalyzer.ZSM-57 can provide the high product selectivity to octene under the condition that reduces alkene collateralization product and burst size.In addition, the ZSM-57 catalyzer is to being present in C in addition 4 +Amylene among the OTO has higher reactive behavior relatively.Therefore the productive rate of nonene is improved in the process.In fact, can be by external source to C 4 +Add the productive rate of additional amylene among the OTO with nonene in the raising process.Described oligomerizing can be 80 ℃-400 ℃ in temperature range, be preferably 120 ℃-300 ℃, and most preferably be 150 ℃-280 ℃, pressure range advantageously is 2MPa-15MPa, be preferably 5MPa-10MPa, and alkene hour air speed scope advantageously is 0.1hr -1-3Ohr -1, be preferably 0.5hr -1-15hr -1, and most preferably be 0.75hr -1-8hr -1Condition under carry out.
Fig. 2 has described tripping device 15, and this tripping device 15 is divided into several tripping device 15a, 15b, 15c, 15d and 15e.In one embodiment, tripping device 15a-15e can design according to the following procedure.Tripping device 15b removes amylene and hexene 17b from higher alkene product 16.Described amylene and hexene 17b can and/or also can introduce in the higher alkene reaction unit 14 as fuel.Round-robin amylene and hexene 17b can with C 4 +Thereby cut 12 mixing form more nonene and decane respectively.Tripping device 15c removes heptene 17c, and tripping device 15d removes octene 17d, and tripping device 15e removes nonene 17e.Also can use other tripping device and separate remaining higher alkene product.What for example, may wish is from C 10-C 20Isolate a large amount of laurylenes in the higher alkene 19, thereby produce C 13Alcohol.C 10-C 20 Higher alkene 19 also can be as other valuable Industrial products chemical feedstocks of jet fuel or high-quality solvent for example.Separate can be applied in method as known in the art and carry out by the number of carbon, as at Kirk-Othmer, " chemical industry encyclopedia " (Encyclopedia of Chemical Technology), the 4th edition, the 20th volume, John Wiley ﹠amp; Sons states in 1996, and disclosure wherein is here as with reference to introducing.
Because C 4 +OTO mainly contains butylene, and the product that expection comes from the higher alkene device will mainly contain octene (about 70%), laurylene (about 17%) and some nonenes (about 5%) and C 16-C 20Alkene (about 5%).These per-cents will be along with the compositions of the type of employed oligomerizing catalyzer and hydrocarbon charging and are changed.
By the more nonenes of higher alkene device production may also be desirable.A kind of method of finishing this task is to add more C in the higher alkene device 5Alkene.C 5The source of alkene can be a small amount of C that steam cracking furnace or higher alkene device are produced 5More C 5Alkene also can be by catalytic cracking higher alkene product such as heptane and C 10-C 20Alkene obtains.
After the higher alkene product was separated into desirable higher alkene component according to the number of carbon, the higher alkene after the various separation can be incorporated in one or more hydroformylation devices.In one embodiment, octene and nonene can be incorporated in the hydroformylation device, produce nonyl alcohol and decyl alcohol respectively.Remaining higher alkene product, the higher alkene that promptly has ten or more a plurality of carbon can be incorporated in the hydrogenation unit.Product behind the hydrogenation can be as blending ingredients to improve the quality of diesel oil or aviation fuel.Octene and nonene that part is not incorporated in the hydroformylation device also can be incorporated in the hydrogenation unit.
A kind of adaptable hydroformylation process is referred to as method for oxidation usually.In method for oxidation, alkene and carbon monoxide and hydrogen react under the temperature and pressure that raises when catalyzer exists, and are terminal aldose or positive aldehyde and centre or branched chain aldehyde thereby produce two kinds of main isomery aldehyde.Alkene, catalyzer, solvent and reaction conditions are depended in the position of formyl radical in the aldehyde product.When using the catalyzer that has the strict complex coordination body that limits such as uncle's phosphuret-(t)ed hydrogen usually, can mainly form positive aldehyde.In most of commercial runs, the initial aldehyde product that forms does not separate.But aldehyde further is converted into alcohol by hydrogenation process or by acetal (aldolization)/hydrogenation process.The purifying of high-molecular weight alcohol generally includes low-pressure distillation or comprises the sepn process of falling-film evaporator.
The equal catalyzed alkene of multiple transition metal changes into aldehyde, but has only the complex compound of cobalt and rhodium to be used for industrial oxidation unit usually.The industrial method for oxidation that relates to conventional cobalt catalyst may comprise following steps at least: hydroformylation promptly forms the refining of refining, the hydrogenation of removing of aldehyde, catalyzer and recovery, aldehyde and last alcohol.In addition, described full scale plant can be used acetal/hydrogenation process aldehyde is changed into alcohol.Commercial hydroformylation is reflected in back-mixing or the tubular type stainless steel reactor or in the two the combination carries out continuously.In backmixed reactor, the composition of reaction mixture is a constant and approaching with the composition of product.In tubular reactor, because piston flow passes through long and narrow pipeline, it forms in time variation continuously.Charging changes reaction conditions according to alkene, but is generally 100 ℃-180 ℃ and 20MPa-35MPa.Applied pressure is decided by the stability of catalyzer under the specific temperature of reaction.Usually the catalyst concn that with alkene is benchmark is about the 0.1%-1% cobalt, and liquid residence time is 1-2 hour.
Thick formoxy-ization changes into alcohol and realizes by heterogeneous gas phase or liquid-phase hydrogenatin in fixed-bed reactor.The metal that has been used as the catalyzer of these hydrogenation processes has the various combinations of copper, nickel, tungsten, cobalt, molybdenum sulphide and these metals.Because sulfur poisoning is not a problem in the present invention, catalyzer nickeliferous or cobalt is preferred.Described catalyzer often places on the inert support by respective metal oxide compound and H-H reaction.
The hydrogenation of oxygenated products carries out under 100 ℃-250 ℃ usually; Actual conditions is decided by applied catalyzer and desirable transformation efficiency.Gas phase process is under low pressure operated, and liquid phase cracking process is operated under the pressure of 35MPa at the most.Need inside or exterior cooling, perhaps the both needs, thereby removes reaction heat.
Application can obviously be improved the selectivity of hydroformylation to the terminal aldose of more wishing by the cobalt carbonyl catalyst of organic phosphuret-(t)ed hydrogen ligand modification, and these terminal aldoses form terminal alcohol conversely probably.Although the cobalt catalyst of these phosphuret-(t)ed hydrogen modifications compared with the cobalt-carbonyl of not complexing reactive behavior a little less than, they can be in higher temperature of reaction, promptly 150 ℃-210 ℃, and lower pressure 2MPa-10MPa uses down.These catalyzer also are active hydrogenation catalysts.Therefore hydroformylation step and many hydrogenation steps take place in same reactor, thereby if in the charging synthetic gas H 2Be about 2: the 1 main alcohol that produce with the ratio of CO.This single step process and catalyzer might be prepared the alcohol of high straight chain/side chain ratio by middle and terminal mixture of linear olefins to the strong preferred property of the reaction on the normal olefine terminal position.
Utilization also is favourable by the rhodium carbonyl catalyst of ligand modification to the formation of linear chain aldehyde.Usually the composition of complex catalyst contains the rhodium of 50ppm-150ppm.About the out of Memory of industrial method for oxidation at Kirk-Othmer, " chemical industry encyclopedia " (Encyclopediaof Chemical Technology), the 3rd edition, the 16th volume, John Wiley ﹠amp; Sons states in the .637-653 page or leaf.
C of the present invention 4 +OTO produces to the process of alkene at oxide compound.Described oxide compound to the process of alkene use pore zeolite or non-zeolite molecular sieve catalyst come the catalyzed oxidation thing for example methyl alcohol make it mainly to be converted into C 2-C 4 +Alkene.Zeolite molecular sieve is complicated aluminosilicate crystal, and it forms an AlO who connects by shared Sauerstoffatom 2 -And SiO 2Tetrahedral network.Tetrahedral negative electricity is by foreign cations such as alkali or alkaline-earth metal ions balance.In some prepare zeolite, in building-up process, there are non-metal cations such as tetramethyl-ammonium (TMA) or tetrapropyl ammonium (TPA).
Zeolite comprises the material that contains silicon-dioxide and optional aluminum oxide, and wherein silicon-dioxide and aluminum oxide are all or part of by other oxide compound alternate material.For example germanium oxide compound, tin-oxide and composition thereof can replace the silicon-dioxide part.Boron oxide compound, ferriferous oxide, gallium oxide, indium oxide and composition thereof can replace the aluminum oxide part.If not indicated otherwise, applied here term " zeolite " and " zeolitic material " will not only refer to contain the material of Siliciumatom and optional aluminium atom in its crystalline network, and refer to contain the material of the suitable substitution atoms of these silicon and aluminium atom.
Nonzeolite, silicoaluminophosphamolecular molecular sieve are preferred for the present invention.These sieves generally include [SiO 2], [AlO 2] and [PO 2] dimensional microporous crystal framework structure of tetrahedron element.Generally speaking, silicoaluminophosphamolecular molecular sieve comprises shared bight [SiO 2], [AlO 2] and [PO 2] the molecular skeleton of tetrahedron element.This class skeleton is effective when making various oxygenate conversion for olefin product.
Preferably be used for silicoaluminophosphamolecular molecular sieve of the present invention and have low relatively Si/Al 2Ratio.Generally speaking, Si/Al 2Lower than more, C 1-C 4The selectivity of stable hydrocarbon particularly selectivity of both propane is low more.Si/Al 2Wish Si/Al than being lower than 0.65 2Than being not more than 0.40 is preferred, and Si/Al 2Than being not more than 0.32 is particularly preferred.Si/Al 2Than being not more than 0.20 is most preferred.
Silicoaluminophosphamolecular molecular sieve is divided into the poromerics with 8,10 or 12 ring structures usually.The average cell size scope of these ring structures can be about 3.5-15 dust.Preferably average cell size is less than the aperture SAPO molecular sieve of about 5 dusts, and described average cell size scope is preferably about 3.5-5 dust, more preferably 3.5-4.2 dust.These hole dimensions are generally the size of the molecular sieve with 8 yuan of rings.
The SAPO that replaces also can be used for the present invention.These compounds are commonly referred to MeAPSO or metallic aluminosilicophosphate.Described metal can be basic metal (IA family), alkaline-earth metal (IIA family), rare earth metal (IIIB family comprises lanthanon), and the transition metal of IB, IIB, IVB, VB, VIB, VIIB and VIIIB family.Usually by in sieve synthesis procedure, adding the metal group bond component of assigning to.But also can use the ion-exchange after synthetic, as among the US 5,962,762 of Sun etc. and disclosed in the u.s. patent application serial number 09/615,526, the disclosure of these documents is here as with reference to introducing.
Suitable silicoaluminophosphamolecular molecular sieve comprises SAPO-5, SAPO-8, SAPO-11, SAPO-16, SAPO-17, SAPO-18, SAPO-20, SAPO-31, SAPO-34, SAPO-35, SAPO-36, SAPO-37, SAPO-40, SAPO-41, SAPO-42, SAPO-44, SAPO-47, SAPO-56, its metallic form and composition thereof.Be preferably SAPO-17, SAPO-18, SAPO-34, SAPO-35, SAPO-44 and SAPO-47, particularly SAPO-17, SAPO-18, SAPO-34, comprise its metallic form and composition thereof.Here applied term mixture is the synonym of composition, and is considered to have two or more compositions according to the material of the component of different ratios, no matter the physical condition of these components how.
Silicoaluminophosphamolecular molecular sieve synthesizes by the common known hydrothermal crystallization methods in this area.For example referring to US 4,440,871, US 4,861,743, US 5,096,684 and US5,126,308, the preparation method of these documents is here all as with reference to introducing.By being mixed, reactive silicon, aluminium and phosphorus component and at least a template form reaction mixture.Common described mixture is preferably sealed and be heated at least 100 ℃ temperature under autogenous pressure, is preferably 100-250 ℃, up to forming crystal product.The formation of crystal product may spend the about 2 hours time to 2 weeks.In some cases, stir or help the formation of product with crystalline material adding crystal seed.
The application combination template can effectively be controlled the structure of SAPO molecular sieve.For example, in a kind of particularly preferred embodiment, the gang form that the SAPO molecular sieve is used TEAOH and dipropyl amine prepares.Thisly be combined to form that particularly methyl alcohol and dimethyl ether conversion are special SAPO structure of wishing light olefin such as ethene and the propylene concerning oxide compound.
Common and other material mixing (being blend) of silicoaluminophosphamolecular molecular sieve.After blend, formed composition is commonly referred to the SAPO catalyzer, promptly includes the catalyzer of SAPO molecular sieve.
Can various inertia or catalytically active material with the material of molecular sieve blend, or various adhesive material.These materials comprise composition such as kaolin and other clay, various forms of rare earth metal, metal oxide, other non-zeolite catalysts component, zeolite catalyst components, aluminum oxide or alumina sol, titanium dioxide, zirconium white, magnesium oxide, thorium dioxide, beryllium oxide, quartz, silica or silicon-dioxide or silicon dioxide gel and composition thereof.These components also are effective especially reducing the total cost of catalyzer, being beneficial to the thermoshield catalyzer, increasing catalyst density and increase aspect the intensity of catalyzer as heat-absorbing body in regenerative process.Special what wish is that the thermal capacitance that is used as the inert material of heat-absorbing body in catalyzer is about 0.05 to about 1cal/g ℃, more preferably about 0.1 to about 0.8cal/g ℃, most preferably is about 0.1 to about 0.5cal/g ℃.
Described catalytic composition preferably contains the 1wt% that has an appointment to about 99wt%, and more preferably about 5wt% most preferably is about 10wt% to about 80wt% molecular sieve to about 90wt%.Preferably the granularity of described catalyst composition is about 20 μ-3,000 μ in addition, and more preferably about 30 μ-200 μ most preferably is about 50 μ-150 μ.
The reactor assembly of any standard may be used to the process of oxide compound to alkene, comprises fixed bed, fluidized-bed or moving-bed system.Preferred reactor is and stream riser reactor and short contacting time adverse current free-falling reactor.Desirable is that oxide raw material can be at least about 1hr at the little hourly space velocity of weight (WHSV) with molecular sieve catalyst in the described reactor -1Following contact, preferable range is about 1hr -1To about 1000hr -1, preferred scope is about 20hr -1To about 1000hr -1, and most preferred scope is about 20hr -1To about 500hr -1WHSV per hour is defined as the oxide compound of catalyzer unit weight molecular sieve here and can chooses the weight that is included in the hydrocarbon in the charging wantonly.Because catalyzer or raw material can contain other material as inert substance or thinner, so WHSV is that benchmark calculates with the weight of oxide compound charging, the hydrocarbon that may exist and the molecular sieve that comprises in catalyzer.
The oxide compound charging is contacted with catalyzer.This method can be carried out in liquid phase or gas/liquid mixed phase in addition.When this method is carried out, may reach different raw material transformation efficiency and selectivity to product according to catalyzer and reaction conditions in liquid phase or gas/liquid mixed phase.
This method can be carried out in wide temperature range usually.Effectively operating temperature range can be about 200 ℃ to about 700 ℃, is preferably about 300 ℃ to about 600 ℃, more preferably about 350 ℃ to about 550 ℃.In the low-temperature end of described temperature range, the formation of desirable olefin product may be obviously slack-off.And in the temperature end of described temperature range, this method may not can form best product volume.
Described pressure also can change in wide scope, comprises autogenous pressure.Efficient pressure can for oxide compound at 7kPa at least, be preferably the dividing potential drop under the 35kPa at least, but need not be confined to this.Under the condition of dividing potential drop greater than 140kPa of higher oxide compound dividing potential drop such as oxide compound, this method is effective especially.The dividing potential drop of described oxide compound is preferably at least about 175kPa, more preferably at least about 210kPa.For the purpose of actual design, hope is no more than under about 3500kPa in the methyl alcohol dividing potential drop and operates, and preferably is no more than about 2800kPa, more preferably no more than about 2100kPa.
Conversion oxide can be carried out in various catalyticreactors with the preparation light olefin.The type of described reactor comprises popular response device such as fixed-bed reactor.Fluidized-bed reactor and riser reactor.Preferred reactor is a riser reactor.
Described the present invention now fully, those skilled in the art are to be appreciated that under the situation that does not depart from the spirit and scope of the invention the present invention can carry out in the defined very wide parameter area of claims.

Claims (19)

1. one kind prepares the method for alkene derivatives by oxide compound, comprising:
Oxide compound is contacted with molecular sieve catalyst, thereby produce the hydrocarbon product that contains alkene;
From hydrocarbon product, isolate the C that contains four or more a plurality of carbon 4 +Cut;
Make C 4 +Cut contacts with the oligomerizing catalyzer, thereby produces product and the purge stream that contains higher alkene; And
The part purge stream is contacted with the oligomerizing catalyzer.
2. the process of claim 1 wherein described C 4 +Cut contains the butylene and about 3wt% butane to about 20wt% of 80wt% to about 97wt% of having an appointment.
3. the method for claim 2, wherein said butylene contain the 20wt% that has an appointment to the 1-butylene of about 40wt% and the about 60wt% 2-butylene of about 80wt% extremely.
4. the process of claim 1 wherein that described olefin product contains the various impurity that are lower than 20ppmw weight, described various impurity are selected from hydrogen sulfide, carbon oxysulfide and arsenic.
5. the process of claim 1 wherein that described molecular sieve catalyst is selected from SAPO-17, SAPO-18, SAPO-34, SAPO-35, SAPO-44, SAPO-56, ZSM-5, ZSM-22, ZSM-35, the metallic form of these materials and composition thereof.
6. the process of claim 1 wherein that the oligomerizing catalyzer is selected from nickel-aluminum alkyls, solid phosphoric acid, nickel-oxide compound and ZSM-57.
7. the method for claim 1 comprises that further the product that makes part contain higher alkene contacts with hydroformylation catalysts.
8. the method for claim 1 further comprises from the product that contains higher alkene and isolates octene, and the part octene is contacted with hydroformylation catalysts to form nonyl alcohol.
9. the method for claim 1 further comprises from the product that contains higher alkene and isolates nonene, and the part nonene is contacted with hydroformylation catalysts to form decyl alcohol.
10. the method for claim 1 further comprises from the product that contains higher alkene and isolates laurylene, and the part laurylene is contacted with hydrogenation catalyst to form dodecane.
11. a compositions of olefines contains:
The 60-80wt% octene;
The 2-10wt% nonene; And
The 8-25wt% laurylene.
12. profit requires 11 compositions of olefines, further contains the alkene that contains 16-20 carbon atom of 2-10wt%.
13. the compositions of olefines of claim 11, the side chain number of wherein said compositions of olefines is lower than 2.0.
14. the compositions of olefines of claim 11, wherein the average side chain number of octene is lower than 1.4.
15. the compositions of olefines of claim 11, wherein the average side chain number of nonene is lower than 1.5.
16. the compositions of olefines of claim 11, wherein the average side chain number of laurylene is lower than 1.8.
17. the compositions of olefines of claim 11, wherein said compositions of olefines contain the alpha-olefin of 10wt% to about 50wt% of having an appointment.
18. the compositions of olefines of claim 11, wherein octene contains the 1-octene of 60wt% to about 95wt% of having an appointment.
19. the compositions of olefines of claim 18, wherein said octene contain the 2-octene of 5wt% to about 30wt% of having an appointment.
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